process for the production of bio-naphtha from complex mixtures of natural occurring fats &amp; oils

ABSTRACT

Process for making a bio-diesel and a bio-naphtha and optionally bio-propane from a complex mixture of natural occurring fats &amp; oils, wherein
         said complex mixture is subjected to a refining treatment for removing the major part of the non-triglyceride and non-fatty acid components, thereby obtaining refined oils;   said refined oils are subjected to a fractionation step for obtaining:
           an unsaturated or substantially unsaturated, liquid or substantially liquid triglyceride part (phase L); and   a saturated or substantially saturated, solid or substantially solid triglyceride part (phase S); and   
           said phase L is transformed into alkyl-esters as bio-diesel by a transesterification;   said phase S is transformed into linear or substantially linear paraffin&#39;s as the bio-naphtha:
           by an hydrodeoxygenation   or from said phase S are obtained fatty acids that are transformed into linear or substantially linear paraffin&#39;s as the bio-naphtha by hydrodeoxygenation or decarboxylation of the free fatty acids or from said phase S are obtained fatty acids soaps that are transformed into linear or substantially linear paraffin&#39;s as the bio-naphtha by decarboxylation of the soaps.

FIELD OF THE INVENTION

The present invention relates to the production of bio-naphtha andbio-distillates in an integrated bio-refinery from complex mixtures ofnatural occurring fats & oils. The limited supply and increasing cost ofcrude oil and the need to reduce emission of fossil based carbondioxides has prompted the search for alternative processes for producinghydrocarbon products such as bio-naphtha and bio-diesel. The bio-naphthacan be used as feedstock of conventional steamcracking. Made up oforganic matter from living organisms, biomass is the world's leadingrenewable energy source.

In the following, “bio-diesel” is sometimes referred to as“bio-distillates”

BACKGROUND OF THE INVENTION

Made from renewable sources, bio-distillates as an alternative fuel fordiesel engines is becoming increasingly important. In addition tomeeting engine performance and emissions criteria/specifications,bio-distillates has to compete economically with petroleum-distillatesand should not compete with food applications for the sametriglycerides. Vegetable oils partially or fully refined and ofedible-grade quality, are currently predominant feedstock for bio-dieselproduction. The prices of these oils are relatively high for fuel-gradecommodities.

These considerations have led to efforts to identify less expensivematerials that could serve as feedstock for bio-diesel production and todesign chemical processes for their conversion. Thus, animal fats havebeen converted to bio-diesel [C. L. Peterson, D. L. Reece, B. L.Hammond, J. Thompson, S. M. Beck, “processing, characterization andperformance of eight fuels from lipids”, Applied Engineering inAgriculture. Vol. 13(1), 71-79, 1997; F. Ma, L. D. Clements and M. A.Hanna, “The effect of catalyst, free fatty acids and water ontransesterification of beef tallow”, Trans ASAE 41 (5) (1998), pp.1261-1264], and substantial efforts have been devoted to the developmentof waste restaurant grease [M. Canakci and J. Van Gerpen,“Bio-destillates production from oils and fats with high free fattyacids”, Trans. ASAE 44 (2001), pp. 1429-1436; Y. Zhang, M. A. Dube, D.D. McLean and M. Kates, “Bio-destillates production from waste cookingoil. 1. Process design and technological assessment”, Bioresour.Technol. 89 (2003), pp. 1-16; W.-H. Wu, T. A. Foglia, W. N. Manner, R.O. Dunn, C. E. Goering and T. E. Briggs, J. Am. Oil Chem. Soc. 75 (1998)(9), p. 1173], largely the spent product of the deep fat frying offoods, as a bio-diesel feedstock.

The industrial chemistry of fats & oils is a mature technology, withdecades of experience and continuous improvements over currentpractices. Natural fats & oils consist mainly of triglycerides and tosome extent of free fatty acids (FFA). Many different types oftriglycerides are produced in nature, either from vegetable as fromanimal origin. Fatty acids in fats & oils are found esterified toglycerol (triacylglycerol). The acyl-group is a long-chain (C₁₂-C₂₂)hydrocarbon with a carboxyl-group at the end that is generallyesterified with glycerol. Fats & oils are characterized by the chemicalcomposition and structure of its fatty acid moiety. The fatty acidmoiety can be saturated or contain one or more double bonds. Bulkproperties of fats & oils are often specified as “saponificationnumber”, “Iodine Value”, “unsaponification number”. The “saponificationnumber”, which is expressed as grams of fat saponified by one mole ofpotassium hydroxide, is an indication of the average molecular weightand hence chain length. The “Iodine value”, which is expressed as theweight percent of iodine consumed by the fat in a reaction with iodinemonochloride, is an index of unsaturation.

Some typical sources of fats & oils and respective composition in fattyacids are given by way of example in Table 1.

TABLE 1 Symbol Cotton- Coconut Corn Palm Peanut Palm Linseed Rice Rape-Olive Saturated Caproic  6:0 0.4 0.2 Caprylic  8:0 7.3 3.3 Capric 10:06.6 3.5 Lauric 12:0 47.8 47.8 0.2 Myristic 14:0 0.9 18.1 16.3 0.1 1.10.4 0.02 Palmitic 16:0 24.7 8.9 10.9 8.5 11.6 44.1 6.0 19.8 3.9 10.5Margaric 17:0 0.05 Stearic 18:0 2.3 2.7 1.8 2.4 3.1 4.4 2.5 1.9 1.9 2.6Arachidic 20:0 0.1 0.1 1.5 0.2 0.5 0.9 0.6 0.4 Behenic 22:0 3.0 0.3 0.20.2 Lignoceric 24:0 1.0 0.2 0.1 TOTAL 28.0 91.9 22.7 82.0 20.3 50 9.023.3 6.8 13.87 Unsaturated Myristoleic 14:1 w-5 Palmitoleic 16:1 w-7 0.70.5 0.1 0.2 0.6 Heptadecenoic 17:1 w-15 0.09 Oleic 18:1 w-9 17.6 6.424.2 15.4 38.0 37.5 19.0 42.3 64.1 76.9 Linoleic 18:2 w-6 53.3 1.6 58.02.4 41.0 10 24.1 31.9 18.7 7.5 Linolenic 18:3 w-3 0.3 0.7 47.4 1.2 9.20.6 Gadolenic 20:1 w-9 1.0 0.5 0.5 1.0 0.3 TOTAL 72.0 8.1 77.3 18.0 79.750 91 76.7 93.2 86.13 Polyunsaturated Ricinoleic 18 Rosin acids — % FFA0.5-0.6 1.0-3.5 1.7 0.1 0.8 2-14 2 5-15 0.5-3.8 0.5-3.3 Soy- Sun- LinolaLard Butterfat Tallow Tall Castor Jatropha Saturated Caproic 2 Caprylic2 Capric 3 Lauric 0.5 0.5 3.5 Myristic 0.1 0.2 1.5 11 3 Palmitic 11.06.8 5.6 26 26 26 2 1.0 14.6 Margaric 0.5 0.5 Stearic 4.0 4.7 4.0 13.5 1122.5 1 1.0 7.4 Arachidic 0.3 0.4 2 0.5 Behenic 0.1 Lignoceric TOTAL 15.512.6 9.6 42.0 60.5 52.0 3.5 2.0 22.0 Unsaturated Myristoleic 0.5Palmitoleic 0.1 0.1 4 2 2.5 0.8 Heptadecenoic 0.5 3 0.5 Oleic 23.4 18.615.9 43 26 43 16 3.0 47.5 Linoleic 53.2 68.2 71.8 9 2.5 1.5 20 4.2 28.7Linolenic 7.8 0.5 2.0 0.5 4 0.3 1.0 Gadolenic 1 0.5 TOTAL 84.5 87.4 90.458.0 37.5 48.0 54.5 7.5 78.0 Polyunsaturated 2 4 Ricinoleic 89.5 Rosinacids 40 % FFA 0.3-1.6 0.1-1.5 0.3 0.5 5-20

Bio-distillates feedstock are classified based on their free fatty acid(FFA) content as follows [J. A. Kinast, “Production of bio-distillatesfrom multiple feedstock and properties of bio-distillates andbio-distillates/-distillates blends”, NREL/SR-5,0-31460 report (2003)]:

-   -   Refined oils, such as soybean or refined canola oils (FFA        <1.5%);    -   Low free fatty acid yellow greases and animal fats (FFA <4.0%);    -   High free fatty acid greases and animal fats (FFA >20.0%).

Bio-diesel is currently produced by transesterification of triglyceridewith methanol, producing methyl-ester and glycerol. Thistransesterification is catalyzed by homogeneous or heterogeneous basiccatalyst. Typically homogeneous catalyst are alkali hydroxides or alkalialkoxides and typical heterogeneous catalyst are alkaline earth or zincoxide materials, like zinc or magnesium-aluminate spinels. The presenceof free fatty acids (FFA) in the raw triglycerides is a cumbersome forthe production of bio-diesel as the FFA's react stoechiometrically withthe basic catalyst producing alkali or alkaline soaps. This means thatfats & oils that contain significant amounts of FFA's cannot be employeddirectly for bio-diesel production with this process. Several technicalsolutions have been proposed: (i) starting with an acid catalysedinteresterification with additional glycerol to convert FFA's intoglycerides prior to the basic transesterification; (ii) prior to thebasic catalyzed transesterification the FFA's are removed by steamand/or vacuum distillation. The latter results in a net loss offeedstock for the production of bio-diesel. Eventually, the so producedFFA's can be converted by acid catalysis into esters in a separateprocess unit. FFA's can be present in triglycerides in differentconcentrations and can be present as such resulting from the extractionprocess or can be produced during storage as of the presence of traceamounts of lipase enzyme that catalyse the triglyceride hydrolysis orcan be produced during processing, like thermal treatments duringcooking.

There are other potential feedstock available at this time, namely trapand sewage grease and other very high free fatty acid greases who's FFAcan exceed 50%.

The main sources of fats & oils are palm and palm kernels, soybeans,rapeseed, sunflower, coconut, corn, animal fats, milk fats.

Potentially new sources of triglycerides will become available in thenear future, namely those extracted from Jatropha and those produced bymicroalgues. These microalgues can accumulate more then 30 wt % oflipids on dry basis and they can either be cultivated in open basin,using atmospheric CO₂ or in closed photobioreactors. In the latter case,the required CO₂ can originate from the use of fossil hydrocarbons thatare captured and injected into the photobioreactor. Main sources offossil CO₂ are power stations, boilers used in refineries andsteamcrackers furnaces used to bring hydrocarbon streams at hightemperature or to supply heat of reactions in hydrocarbontransformations in refineries and steamcrackers. In particularsteamcracking furnaces produce a lot of CO₂. In order to enhance the CO₂concentration in flue gases of these furnaces, techniques likeoxycombustion, chemical looping or absorption of CO₂ can be employed. Inoxycombustion, oxygen is extracted from air and this pure oxygen is usedto burn hydrocarbon fuels as to obtain a stream only containing waterand CO₂, allowing concentrating easily the CO₂ for storage orre-utilisation. In chemical looping, a solid material acts asoxygen-transfer agent from a re-oxidation zone where the reduced solidis re-oxidised with air into oxidised solid to a combustion zone, wherethe hydrocarbon fuel is burned with the oxidised solid and hence theeffluent resulting from the combustion zone only contains water and CO₂.Absorption of CO₂ can be done with the help of a lean solvent that has ahigh preferential to absorb CO₂ under pressure and typically at lowtemperature and will release the CO₂ when depressurised and/or heated.Rectisol® and Selexol® are commercial available technologies to removeand concentrate CO₂. Other sources of CO₂ are the byproduct fromcarbohydrates fermentation into ethanol or other alcohols and theremoval of excess CO₂ from synthesis gas made from biomass or coalgasification.

US 2007/0175795 reports the contacting of a hydrocarbon and atriglyceride to form a mixture and contacting the mixture with ahydrotreating catalyst in a fixed bed reactor under conditionssufficient to produce a reaction product containing diesel boiling rangehydrocarbons. The example demonstrates that the hydrotreatment of suchmixture increases the cloud point and pour point of the resultinghydrocarbon mixture.

US 2004/0230085 reports a process for producing a hydrocarbon componentof biological origin, characterized in that the process comprises atleast two steps, the first one of which is a hydrodeoxygenation step andthe second one is an isomerisation step. The resulting products have lowsolidification points and high cetane number and can be used as dieselor as solvent.

US 2007/0135669 reports the manufacture of branched saturatedhydrocarbons, characterized in that a feedstock comprising unsaturatedfatty acids or fatty acids esters with C1-C5 alcohols, or mixturethereof, is subjected to a skeletal isomerisation step followed by adeoxygenation step. The results demonstrate that very good cloud pointscan be obtained. US 2007/0039240 reports on a process for crackingtallow into diesel fuel comprising: thermally cracking the tallow in acracking vessel at a temperature of 260-371° C., at ambient pressure andin the absence of a catalyst to yield in part cracked hydrocarbons.

U.S. Pat. No. 4,554,397 reports on a process for manufacturing olefins,comprising contacting a carboxylic acid or a carboxylic ester with acatalyst at a temperature of 200-400° C., wherein the catalystsimultaneously contains nickel and at least one metal from the groupconsisting of tin, germanium and lead.

It has been discovered a process to make bio-naphtha and bio-diesel inan integrated biorefinery from all kinds of natural triglycerides orfatty acids. In said process crude fats & oils are refined, eitherphysically or chemically, to remove all non-triglyceride and non-fattyacid components. The refined oils are next fractionated in both liquidand solid fractions. This process aims at separating a starting materialinto a low melting fraction, the liquid fraction, consisting oftriglycerides, having double bonds in the acyl-moieties and a highmelting fraction the solid fraction, consisting of substantiallysaturated acyl-moieties. This process allows optimising the use of thedifferent molecules constituting the natural fats & oils.Bio-destillates require specific cold-flow properties that requiresdouble bonds in the acyl-moiety. On the other hand, the quality of asteamcracker feedstock is better when the hydrocarbon is saturated andlinear.

The liquid fraction, potentially mixed with some limited solid fraction,is transesterified with a C₁ to C₅ monofunctional alcohol to producealkyl fatty esters, called also bio-diesel, and glycerol. The amount ofsolid fraction should be so that the final cold-flow properties areaccording to the local market specifications.

The solid fraction, potentially mixed with some liquid fraction, can beconverted to produce bio-naphtha and optionally bio-propane. The solidfraction can be directly hydrodeoxygenated or can also be hydrolyzed togive fatty acids, potentially mixed with those produced during refining.Then fatty acids can be hydrodeoxygenated or decarboxylated tobio-naphtha. The solid fraction can also be saponified to produceglycerol and soap that can subsequently be decarboxylated.

As several sources of fats & oils are not suitable to be converted inester-type bio-diesel because they contain too much saturatedacyl-moieties that result in high pour-points and hence impropercold-flow properties, the present invention solves this problem by anappropriate separation of the starting complex mixtures, allowing anoptimal usage of fats & oils for making bio-diesel and bio-naphtha.

The use of a biofeed is a possible solution in the search of alternativeraw material for the naphthacracker. Nevertheless, using this type offeed can lead to corrosion problems and excessive fouling because ofoxygenates forming from the oxygen atoms in the biofeed. Also existingsteamcrackers are not designed to remove high amounts of carbonoxidesthat would result from the steameracking of these biofeedstock.According to the present invention, such a problem can be solved byhydrodeoxygenating/decarboxylating (or decarbonylating) this biofeedbefore its injection into the steam cracker. Thanks to thishydrodeoxygenation/decarboxylation (or decarbonylation), the negativeeffect due to the production of CO and CO₂ and traces of low molecularweight oxygenates (aldehydes and acids) in the steam cracker is reduced.

Another advantage is of course the production of bio-monomers in thesteam cracker.

BRIEF DESCRIPTION OF THE INVENTION

The subject-matter of the present invention is in an embodiment 1 aprocess for making a bio-diesel and a bio-naphtha from a complex mixtureof natural occurring fats & oils, wherein

-   -   said complex mixture is subjected to a refining treatment for        removing the major part of the non-triglyceride and non-fatty        acid components, thereby obtaining refined oils;    -   said refined oils are subjected to a fractionation step for        obtaining:        -   an unsaturated or substantially unsaturated, liquid or            substantially liquid triglyceride part (phase L); and        -   a saturated or substantially saturated, solid or            substantially solid triglyceride part (phase S); and    -   said phase L is transformed into alkyl-esters as bio-diesel by a        transesterification;    -   said phase S is transformed into linear or substantially linear        paraffin's as the bio-naphtha:        -   by an hydrodeoxygenation        -   or from said phase S are obtained fatty acids that are            transformed into linear or substantially linear paraffin's            as the bio-naphtha by hydrodeoxygenation or decarboxylation            of the free fatty acids        -   or from said phase S are obtained fatty acids soaps that are            transformed into linear or substantially linear paraffin's            as the bio-naphtha by decarboxylation of the soaps.

In an embodiment 2 the invention is according to embodiment 1, whereinsaid complex mixture of natural occurring fats & oils is selected amongvegetable oils and animal fats, preferentially inedible oils, highlysaturated oils, waste food oils, by-products of the refining ofvegetable oils, and mixtures thereof.

In an embodiment 3 the invention is according to embodiment 1 or 2,wherein said fatty acids are obtained by physical refining, including asteam distillation or vacuum distillation of fats & oils

-   -   or said fatty acids are obtained by hydrolysis of triglycerides        of the fats & oils    -   or said fatty acids are obtained by acidulation of soaps.

In an embodiment 4 the invention is according to anyone of embodiments 1and 2, wherein said refined oils are fractioned into said phases L and Sby a fractional crystallisation method which consists in a controlledcooling down during which the triglycerides of said complex mixture withsubstantially saturated acyl-moieties crystallize and precipitate fromthe mixture forming said phase S, while the triglycerides withsubstantially unsaturated acyl-moieties remain liquid forming said phaseL, both phases being then separated by simple filtration or decantationor centrifugation.

In an embodiment 5 the invention is according to embodiments 1, 2 and 4,wherein said phase L is transesterified with a C₁-C₅ monofunctionalalcohol in order to produce alkyl fatty esters as bio-diesel andglycerol.

In an embodiment 6 the invention is according to embodiment 1 or 2,wherein said fatty acid soaps are obtained by saponification of fats &oils

-   -   or by the chemical refining, including neutralisation of free        fatty acids, present in the fats & oils    -   or neutralisation of fatty acids, obtained from hydrolysis of        the fats & oils

In an embodiment 7 the invention is according to anyone of embodiments 1to 4, wherein said phase S is transformed into linear or substantiallylinear paraffins as bio-naphtha together with bio-propane byhydrodeoxygenation in the presence of hydrogen and of at least onecatalyst that can be selected among Ni, Mo, Co or mixtures like NiW,NiMo, CoMo, NiCoW, NiCoMo, NiMoW and CoMoW oxides or sulphides ascatalytic phase, preferably supported on high surface area carbon,alumina, silica, titania or zirconia.

In an embodiment 8 the invention is according to embodiment 7, whereinthe hydrodeoxygenation is carried out at a temperature from 200 to 500°C., under a pressure from 1 MPa to 10 MPa (10 to 100 bars) and with ahydrogen to feed ratio from 100 to 2000 N1/1.

In an embodiment 9 the invention is according to anyone of embodiments 1to 4, wherein said phase S is transformed into linear or substantiallylinear paraffins as bio-naphtha by hydrolysis into glycerol and fattyacids, removal of the glycerol or by physical refining, including asteam distillation or vacuum distillation of fats & oils or obtained byacidulation of soaps and hydrodeoxygenation or decarboxylation of thefatty acids, said hydrodeoxygenation or decarboxylation being conductedin the presence of hydrogen and of at least one catalyst that can beselected among Ni, Mo, Co or mixtures like NiW, NiMo, CoMo, NiCoW,NiCoMo, NiMoW and CoMoW oxides or sulphides as catalytic phase,preferably supported on high surface area carbon, alumina, silica,titania or zirconia or group 10 (Ni, Pt and Pd) and group 11 (Cu and Ag)metals or alloy mixtures supported on high surface area carbon,magnesia, zinc-oxide, spinels (Mg₂Al₂O₄, ZnAl₂O₄), perovskites (BaTiO₃,ZnTiO₃), calciumsilicates (like xonotlite), alumina, silica orsilica-alumina's or mixtures of the latter.

In an embodiment 10 the invention is according to anyone of embodiments1 to 4, wherein said phase S is transformed into linear or substantiallylinear paraffin's as bio-naphtha by hydrolysis into glycerol and fattyacids, removal of the glycerol or by physical refining, including asteam distillation or vacuum distillation of fats & oils or obtained byacidulation of soaps and decarboxylation of the fatty acids is carriedout on basic oxides, like alkaline oxides, alkaline earth oxides,lanthanide oxides, zinc-oxide, spinels (Mg₂Al₂O₄, ZnAl₂O₄), perovskites(BaTiO₃, ZnTiO₃), calciumsilicates (like xonotlite), either as bulkmaterial or dispersed on neutral or basic carriers, on basic zeolites(like alkali or alkaline earth low silica/alumina zeolites obtained byexchange or impregnation).

In an embodiment 11 the invention is according to anyone of embodiments7 to 10, wherein the hydrodeoxygenation is carried out at a temperaturefrom 200 to 500° C., under a pressure from 1 MPa to 10 MPa (10 to 100bars) and with a hydrogen to feedstock ratio from 100 to 2000 Nl/l. orwherein the decarboxylation is carried out at a temperature from 100 to550° C., under a pressure from 0.1 MPa to 10 MPa (1 to 100 bars) andwith a hydrogen to feedstock ratio from 0 to 2000 Nl/l.

In an embodiment 12 the invention is according to embodiments 1 to 4 and6, wherein the decarboxylation of the soaps is carried out at from 100to 550° C. under pressure from 0.1 Mpa to 10 Mpa and in presence ofwater.

In an embodiment 13 the invention is according to embodiments 1 to 4 and6, wherein the decarboxylation of the soaps is carried out with a waterto feedstock ratio of at least 1 mole water per mole of soap.

In an embodiment 14 the invention is the Use of the bio-naphtha asobtained in the process of embodiments 1 to 4 and 6 to 13, as a directfeedstock of a steamcracker, said bio-naphtha being used as such, oroptionally together with bio-propane, or as blended with at least aconventional feedstock selected among LPG, naphtha and gasoil, in orderto obtain cracked products including bio-ethylene, bio-propylene,bio-butadiene, bio-isoprene, bio-cyclopentadiene and bio-piperylenes,bio-benzene, bio-toluene, bio-xylene and bio-gasoline.

In an embodiment 15 the invention is a process for steam cracking afeedstock as defined in embodiment 14, wherein said feedstock is mixedwith steam in a ratio of 0.2 to 1.0 kg steam per kg feedstock,preferentially of 0.3 to 0.5 kg steam per kg feedstock and the mixtureis heated up to a temperature of 750-950° C. at a residence time of 0.05to 0.5 seconds.

In an embodiment 16 the invention is the Use of the bio-naphtha asobtained in the process of embodiments 1 to 15 for steamcracking such asto obtain a ethylene to methane weight ratio, resulting from thecracking of bio-naphtha, of at least 3.

By “bio-naphtha” we mean naphtha produced from renewable sources byhydrotreatment of these renewable sources. It is a hydrocarboncomposition, consisting of mainly paraffin's and that can be used forthe steamcracking to produce light olefins, dienes and aromatics. Themolecular weight of this bio-naphtha ranges from hydrocarbons having 8to 24 carbons, preferably from 10 to 18 carbons.

By “substantially linear paraffins”, we mean a composition of paraffin'sconsisting of at least 90% by weight of linear paraffin's.

Said complex mixture of natural occurring fats & oils can be selectedamong vegetable oils and animal fats, preferentially inedible highlysaturated oils, waste food oils, by-products of the refining ofvegetable oils, and mixtures thereof. Specific examples of these fats &oils have been previously mentioned in the present specification.

Said refined fats & oils can be advantageously fractioned into saidphases L and S by a fractional crystallisation method which consists ina controlled cooling down during which the triglycerides of said complexmixture with substantially saturated acyl-moieties crystallize andprecipitate from the mixture forming said phase 5, while thetriglycerides with substantially unsaturated acyl-moieties remain liquidforming said phase L, both phases being then separated by simplefiltration or decantation or centrifugation.

Said phase L can be transesterified with a C₁C₅ monofunctional alcoholin order to produce alkyl fatty esters as bio-diesel and glycerol. Saidalcohol can be methanol.

Said phase S, optionally still containing some free fatty acids can betransformed into linear or substantially linear paraffin's asbio-naphtha together with bio-propane by hydrodeoxygenation in thepresence of hydrogen and of at least one hydrodeoxygenation catalyst Thehydrodeoxygenation catalyst can be selected among Ni, Mo, Co or mixtureslike NiW, NiMo, CoMo, NiCoW, NiCoMo, NiMoW and CoMoW oxides or sulphidesas catalytic active phase, preferably supported on high surface areacarbon, alumina, silica, titania or zirconia or group 10 (Ni, Pt or Pd)or group 11 (Cu or Ag) metals or alloy mixtures supported on highsurface area carbon, magnesia, zinc-oxide, spinels (Mg₂Al₂O₄, ZnAl₂O₄),perovskites (BaTiO₃, ZnTiO₃), calciumsilicates (like xonotlite),alumina, silica or mixtures of the latter. It is preferred that thesupport for the catalytic active phase exhibit low acidity, preferableneutral or basic in order to avoid hydro-isomerisation reactions thatwould result in branched paraffin's and cracking. The hydrodeoxygenationof the fats & oils can be carried out at a temperature from 200 to 500°C., preferably from 280 to 400° C., under a pressure from 1 MPa to 10MPa (10 to 100 bars), for example of 6 MPa, and with a hydrogen torefined oils ratio from 100 to 2000, but preferably from 350 to 1500 forexample of 600 Nl H2/l oil.

Said phase S can also be transformed into linear or substantially linearparaffin's as bio-naphtha by producing fatty acids by (i) hydrolysis ofthe phase S fats & oils into glycerol and fatty acids, removal of theglycerol, by (ii) physical refining (steam/vacuum distillation) of phaseS fats & oils or by acidulation of fatty acid soaps and subsequentlyhydrodeoxygenation or decarboxylation (or decarbonylation) of the fattyacids, or a combination of these processes. Advantageously saidhydrodeoxygenation is conducted in the presence of hydrogen and of atleast one hydrodeoxygenation or decarboxylation catalyst. Thehydrodeoxygenation or decarboxylation catalyst can be selected among Ni,Mo, Co or mixtures like NiW, NiMo, CoMo, NiCoW, NiCoMo, NiMoW and CoMoWoxides or sulphides as catalytic phase, preferably supported on highsurface area carbon, alumina, silica, titania or zirconia or group 10(Ni, Pt or Pd) or group 11 (Cu or Ag) metals or alloy mixtures supportedon high surface area carbon, magnesia, zinc-oxide, spinels (Mg₂Al₂O₄,ZnAl₂O₄), perovskites (BaTiO₃, ZnTiO₃), calciumsilicates (likexonotlite), alumina, silica or silica-alumina's or mixtures of thelatter. It is preferred that the support for the catalytic active phaseexhibit low acidity, preferable neutral or basic in order to avoidhydro-isomerisation reactions that would result in branched paraffin'sand cracking. The hydrolysis (splitting) can be carried out in presencesteam thermally at 15 to 75 bars and at 50-300° C. or catalytically, forexample with basic catalysts, like MgO, CaO, ZnO, spinels (Mg2Al2O4,ZnAl2O4), perovskites (BaTiO3, ZnTiO3), calciumsilicates (likexonotlite) or basic alumina or with acidic catalysts, like sulphuricacid. Detailed information about fat & oil splitting has been publishedby Sonntag (Sonntag, N., J. Am. Oil. Chem. Soc., 56, p. 729, 1979 andBailey's Industrial Oil and Fat Products, ed. F. Shahidi, 2005, JohnWiley & Sons). In the Colgate-Emery process, heated liquid lipid isintroduced at the bottom of a vertical tubular reactor. Heated waterenters at the top. As the fats & oils rises through the descending waterunder pressure, a continuous zone of high water solubility in oilestablishes, wherein hydrolysis occurs. Effluent from the column isrecovered, fatty acids from one outlet and an aqueous glycerol streamfrom the other. The presence of small amounts of mineral acids, such assulfuric acid or sulfonic acids or certain metal oxides, such as zinc ormagnesium oxide, accelerates the splitting reaction. These metal oxidesare true catalysts and they assist also in the formation of emulsions.

The hydrodeoxygenation of the fatty acids can be carried out at atemperature from 200 to 500° C., preferably from 280 to 400° C., under apressure from 1 MPa to 10 MPa (10 to 100 bars), for example of 6 MPa,and with a hydrogen to refined oils ratio from 100 to 2000Nl/l, forexample of 600 Nl H2/l oil. The decarboxylation of the fatty acids canbe carried out at 100 to 550° C. in absence or presence of hydrogen atpressures ranging from 0.01 up to 10 MPa.

Said phase S can also be transformed into linear or substantially linearparaffin's as bio-naphtha by thermal decarboxylation of fatty acidsoaps. These soaps are obtained during chemical refining byneutralisation to convert free fatty acids into soaps, by neutralisationof fatty acids obtained by hydrolysis of phase S fats & oils or bycomplete saponification of phase S triglycerides into glycerol and soap.A soap is a metal salt of the corresponding fatty acid.

The present invention also relates to the use of the bio-naphtha asobtained in the above mentioned process, as a direct feedstock of asteamcracker, said bio-naphtha being used as such, or together with thebio-propane when produced by the above-mentioned process, or as blendedwith at least a conventional feedstock selected among LPG, naphtha andgasoil, in order to obtain cracked products including bio-ethylene,bio-propylene, bio-butadiene, bio-isoprene, bio-(di)cyclopentadiene,bio-piperylenes, bio-benzene, bio-toluene, bio-xylene and bio-gasoline.

Moreover, the present invention relates to a process for steam crackinga feedstock as defined above, wherein said feedstock is mixed withsteam, having a steam/feedstock ratio of at least 0.2 kg per kg offeedstock. This mixture is sent through the heated coils, having a coiloutlet temperature of at least 700° C. and a coil outlet pressure of atleast 1.2 bara.

DETAILED DESCRIPTION OF THE INVENTION

All crude fats & oils obtained after rendering, crushing or solventextraction inevitably contain variable amounts of non-triglyceridecomponents such as free fatty acids, mono and diglycerides,phosphatides, sterols, tocopherols, tocotrienols hydrocarbons, pigments(gossypol, chlorophyll), vitamins (carotenoids), sterols glucosides,glycolipids, protein fragments, traces of pesticides and traces metals,as well as resinous and mucilaginous materials. The quantities of thenon-glycerides vary with the oil source, extraction process, season andgeographical source. Removal of the non-triglyceride components, whichinterfere with further processing and cause the oil to darken, foam,smoke, precipitate and develop off-flavours, is the objective of therefining process.

Refining Pretreatment Choice of the Refining Method

FIG. 1 illustrates the refining pretreatment in which crude oils areprocessed through various routes, physical or chemical, to RefinedBleached Deodorized (RBD) oils. Physical refining and alkali/chemicalrefining differ principally in the way free fatty acids are removed.

In chemical refining, FFA, most of the phosphatides, and otherimpurities are removed during neutralization with an alkaline solution,usually NaOH.

In physical refining, the FFA is removed by distillation duringdeodorization and the phosphatides and other impurities must be removedprior to steam distillation. fats & oils

Currently, the refining method of choice is determined by thecharacteristics of the individual crude fats & oils:

(1) fats and oils that are normally physically refined;

(2) fats and oils that can be physically or chemically refined; and

(3) fats and oils that can only be chemically refined.

Table 2 below summarizes advantages and disadvantages of each treatment:

TABLE 2 Refining type Advantages Disadvantages Chemical Functionalprocess Production of by- refining products Not restricted by theExpensive process oil type Successful reduction High loss of oil of FFAPhysical Cheaper Not suitable for all types refining of oils Lessby-products Requires high temperature and vacuum Less energy Can formundesired side consumed reaction products

Physical Refining

The physical refining can remove the FFA, as well as the unsaponifiablesand other impurities by steam stripping, thus eliminating the productionof soapstock and keeping neutral oil loss to a minimum. However,degumming pretreatments of the crude fats & oils are still required toremove those impurities that darken or otherwise cause a poor-qualityproduct when heated to the temperature required for steam distillation.A degumming process is crucial for physical refining but optional forchemical refining. It consists of the treatment of crude oils, withwater, salt solutions, enzymes, caustic soda, or diluted acids such asphosphoric, citric or maleic to remove phosphatides, waxes, pro-oxidantsand other impurities. The degumming processes convert the phosphatidesto hydrated gums, which are insoluble in oil and readily separated as asludge by settling, filtering or centrifugal action. After degumming,phosphorous must be less than 30 ppm. So that bleaching or dry degummingcan further reduce this level to less than 5 ppm and remove all tracesof iron and copper. Acid or enzymatic degumming processes are normallyemployed to achieve these results.

The various industrial degumming processes have different aims. Fats &oils to be degummed vary widely in gum content and gum properties andfinally, the means of gum disposal available, what equipment is neededand/or available, and the cost of auxiliaries also influence the choiceof the most appropriated degumming process. The lipid handbook (Thelipid handbook, edited by Frank D. Gunstone, John L. Harwood, Albert J.Dijkstra. 3rd ed., chapter 3.4) deals with these aspects in details.Next is briefly described the four major degumming process applied onthe market.

The main purposes of the water degumming process are to produce oil thatdoes not deposit a residue during transportation and storage, and tocontrol the phosphorus content of crude oils just below 200 ppm. Thisprocess involves the addition of live steam to raw oil for a shortperiod. The proper amount of water is normally about 75% of thephosphatides content of the oil. Too little water produces dark viscousgums and hazy oil, while too much water causes excess oil losses throughhydrolysis. Water-degummed oil still contains phosphatides (between 80and 200 ppm); only hydratable phosphatides are removed with thisprocess. The nonhydratable phosphatides, which are calcium and magnesiumsalts of phosphatic acid and phosphatidyl ethanolamine, remain in theoil after water degumming.

Acid degumming process leads to a lower residual phosphorus content thanwater degumming and is therefore a good alternative if dry degumming andphysical refining are to be the next refining steps. The acid degummingprocess might be considered as a variant of the water degumming processin that it uses a combination of water and acid. The non-hydratablephosphatides can be conditioned into hydratable forms with aciddegumming. Phosphoric and citric acids are used because they are foodgrade, sufficiently strong and they bind divalent metal ions. Severalacid degumming processes have been developed to attain a phosphorusvalue lower than 5 ppm that is required for good quality physicallyrefined oils.

An acid refining differs from the acid degumming by the neutralisationof the liberated phosphatides (the action of the degumming acid does notlead to full hydration of the phosphatides) to make them hydratable bythe addition of a base.

In dry degumming process, the oil is treated with an acid (principle isthat strong acids displace weaker acids from their salts) to decomposethe metal ion/phosphatides complex and is then mixed with bleachingearth. The earth containing the degumming acid, phosphatides, pigmentsand other impurities is then removed by filtration. Seed oils that havebeen water or acid-degummed may also be dry degummed to ensure a lowphosphorus oil to steam distillation. An increase in FFA of less than0.2% should be expected but the final phosphorus content must be reducedto less than 5 ppm. This process constitutes the main treatment for palmoil, laurie oils, canola oil and low phosphatides animal fats, such astallow or lard. The dry degumming process allows crude oil to be fullyrefined in only two steps: dry degumming and physical refining.

In enzymatic degumming process, Phospholipase A1, the lastest developeddegumming enzyme, changes the phospholipids into lysophospholipids andfree fatty acids. This process has three important steps:

(1) adjustment of the pH with a buffer;

(2) enzymatic reaction in the holding tanks; and

(3) separation of the sludge from the oil.

Oil to be degummed enzymatically by this way can be crude or waterdegummed.

The lipid handbook (The lipid handbook, edited by Frank D. Gunstone,John L. Harwood, Albert J, Dijkstra. 3rd ed.) describes many variantsand details of the degumming processes.

The purpose of bleaching is to provide a decoloured oil but also topurify it in preparation for further processing. All fully refined oilshave been subjected to one or the other bleaching process. Refined oilcontains traces of a number of undesirable impurities either in solutionor as colloidal suspensions. The bleaching process does more than justincreasing the transmission of light through the oil and is often called“adsorptive cleaning.”. The bleaching process is often the firstfiltration encountered by the oil, so it ensures the removal of soaps,residual phosphatides, trace metals, and some oxidation products, and itcatalyses the decomposition of carotene and the adsorbent also catalysesthe decomposition of peroxides. These non-pigment materials, such assoap, gums, and pro-oxidants metals, which hinder filtration, poisonhydrogenation catalyst, darken the oils, and affect finished oilflavour. Another function is the removal of the peroxides and secondaryoxidation products. The key parameters for the bleaching process areprocedure, adsorbent type and dosage, temperature, time, moisture andfiltration, as shown in the Lipid Handbook (The lipid handbook, editedby Frank D. Gunstone, John L. Harwood, Albert J. Dijkstra. 3rd ed.,chapter 3.7). The three most common types of contact bleaching methodsused for edible fats and oils are batch atmospheric, batch vacuum andcontinuous vacuum. Chemical agents have been used or proposed for usebut practically all edible oil decolouration and purification isaccomplished with adsorptive clays, synthetic amorphous silica andactivated carbons.

Before the last major processing step, bleached oil can be hydrogenated,for two reasons. One reason is to change naturally occurring fats & oilsinto physical forms with the consistency and handling characteristicsrequired for functionality. The second reason for hydrogenation is toincrease the oxidation and thermal stability. Instead of purification inother described processes, this step consists in fats & oils molecularmodification.

Hydrogen is added directly to react with unsaturated oil in the presenceof catalysts, mostly nickel. This process greatly influences the desiredstability and properties of many edible oil products. The hydrogenationprocess is easily controlled and can be stopped at any point. A gradualincrease in the melting point of fats and oils is one of the advantages.If the double bonds are eliminated entirely with hydrogenation, theproduct is a hard brittle solid at room temperature. Shortening andmargarine are typical examples. A wide range of fats and oils productscan be produced with the hydrogenation process depending upon theconditions used, the starting oils, and the degree of saturation orisomerization.

To obtain good-quality fats and oils with physical refining, it isessential to have a phosphorous content lower than 5 ppm before steamstripping.

The degummed-bleached oils are vacuum stripped. This process encompassesthe deodorization process, applied after the alkali routes, as well asphysical refining. Deodorization, the last major processing step duringwhich the FFA can be removed, is a vacuum-steam distillation process(1-2 mbar of residual pressure) at elevated temperature (180-240° C.)during which FFAs and minute levels of odoriferous materials, mostlyarising from oxidation, are removed to obtain a bland and odourless oil.In order to volatilise the undesired high-boiling components, a deepvacuum and dilution with steam is applied so that the boilingtemperature can be minimised. The deodorization utilizes the differencesin volatility between off-flavour and off-odor substances and thetriglycerides.

The odoriferous substances, FFAs, aldehydes, ketones, peroxides,alcohols, and others organic compounds are concentrated in a deodorizerdistillate. Efficient removal of these substances depends upon theirvapour pressure, for a given constituent is a function of thetemperature and increases with the temperature.

As usually the last stage in the refining process, deodorization has animportant effect an overall refined oil quality and distillatecomposition. Its main purposes are giving a bland taste and smell, lowFFA content, high oxidative stability and light and stable colour.Because of the need of a rather high temperature to remove the undesiredcomponents, unwanted side effects are, isomerisation of double bond,polymerisation, intra-esterification and degradation of vitamins andanti-oxidants. New dry condensing (steam is condensed into ice) vacuumsystems capable of reaching a very low operating pressure in thedeodorizer were introduced (close to 0.1 kPa). This progress allows areduction of the deodorization temperature without affecting thestripping efficiency in a negative way. In order to minimise the timethat the oil is at high temperature, deodorizers can operate at dualtemperatures to reach the best compromise between required residencetime for deodorizing (at moderate temperature) and heat bleaching andfinal stripping at high temperature.

Deodorizer distillate is the material collected from the steamdistillation of edible oils. The distillate from physically refined oilsconsists mainly of FFAs with low levels of unsaponifiable components.The concentration of FFA can be improved from typical 80% up to 98% byapplying double condensing system that produces an enriched FFA cut. Thedistillate can be used as a source of industrial fatty acids or mixedwith the fuel oil used to fire the steam boilers.

A physical refining will be preferred due to higher remaining FFAcontent in refined oils before steam stripping.

Chemical Refining

As applied to crude oils, it includes degumming (removal ofphospholipids), neutralization (removal of free fatty acids), bleaching(decolourisation) and deodorization (FIG. 1).

Degumming involves for instance the addition of water to hydrate anygums present, followed by centrifugal separation. Non-hydratable gumsare removed by converting them first to a hydratable form usingphosphoric or citric acid, followed by the addition of water andcentrifugation. Acid degumming can also be used (see the descriptionabove).

The following step is neutralisation in which an aqueous alkali,typically caustic soda or sodium carbonate, is sprayed into the oilwhich has been preheated to around 75-95° C. The alkali reacts with freefatty acids in the oil to form soaps, which are separated by settling orcentrifugation. Selection of the aqueous alkali strength, mixing time,mixing energy, temperature, and the quantity of excess caustic all havean important impact on making the chemical refining process operateefficiently and effectively. A drying step may be incorporated afterneutralisation to ensure the complete removal of the added water. Thesoap can be used as such or can be hydrolysed (acidulation) withsulphuric acid into the corresponding FFA.

The neutralised oil is bleached to remove colouring matter (such ascarotenoids) and other minor constituents, such as oxidative degradationproducts or traces of metals. Bleaching uses activated fuller's earthwith treatments typically in the 90-130° C. range for 10-60 minutes. Theearth is sucked into the oil under vacuum and is removed by filtration.

The bleached oil is steam distilled at low pressure to remove volatileimpurities including undesirable odours and flavours. This process,known as deodorisation, takes place in the temperature range of 180-270°C. and may last 15 minutes to five hours depending upon the nature ofthe oil, the quantity, and the type of equipment used.

Fractionation Treatment into Phases L and S

FIG. 2 illustrates where refined natural triglycerides and fatty acidsare separated in a liquid fraction and a solid fraction, namely phases Land 5, respectively.

The fractionation according to the present invention or “dryfractionation” or “dry winterization” is the removal of solids bycontrolled crystallization and separation techniques involving the useof solvents or dry processing (sometimes also referred to as dewaxing).It relies upon the difference in melting points to separate the oilfractions. The fractionation process has two main stages, the firstbeing the crystallization stage. Crystals grow when the temperature ofthe molten fat & oil or its solution is lowered, and their solubility atthe final or separation temperature determines the triglyceridescomposition of the crystals formed as well as their mother liquor.Separation process is the second step of fractionation. Several optionshave been reported, such as vacuum filters, centrifugal separators,conical screen-scroll centrifuges, hydraulic presses, membrane filterpresses, or decanters with each their own advantages and drawbacks.

Fractionation can occur spontaneously during storage or transport, andthis forms the basis of the dry fractionation process. This process isthe oldest process type and thanks to steadily improved separationmethods it has become competitive on product quality grounds with other,more expensive processes, such as solvent and detergent fractionation.

Fractionation can also been carried out in presence of solvents, likeparaffin's, alkyl-acetates, ethers, ketons, alcohols or chlorinatedhydrocarbons. The use of solvents accelerates the crystallisation andallows to crystallise more material before the slurry can no more behandled.

The term “fractional crystallisation” will be used throughout this textand encompasses winterisation, dry fractionation and solventfractionation.

Raw fats and oils are preatreated e.g. by degumming and bleaching, thenthey can be physically refined (10) by way of example by vacuum or steamdistillation to produce triglycerides (12) at bottoms and mixed fattyacids at overhead (11). optionally all or a part of the preatreated fatsand oils (30) is mixed with the triglycerides (13)and sent to thefractional crystallisation to recover solid and liquid triglycerides asexplained above. The solid triglycerides (41) and the mixed fatty acids(11) and (42) are sent to the bio naphtha production. The liquidtriglycerides (40) are sent to the fatty acid alkyl ether production,optionally to make bio diesel.

Obtention of Bio-Diesel from Phase L

Methylesters are produced from liquid triglycerides bytransesterification with alcohols. If an oil or fat containing a highcontent in free fatty acids is used to produce bio-destillates, thealkali catalyst typically used to accelerate the reaction will reactwith this acid to form soap, according to the following reaction:

C₁₇H₃₃COOH+KOH→C₁₇H₃₃COOK+H₂O

This reaction is undesirable because it binds the catalyst into a formthat does not contribute anymore to accelerating the reaction. Excessivesoap in the products can inhibit later processing of thebio-distillates, including glycerol separation and water washing. Theformation of water, according to the reaction above is also a problem.When water is present, particularly at high temperatures, it canhydrolyze the triglycerides to diglycerides and form a free fatty acid,according to the following reaction:

[C₁₈H₃₃O]₃C₃H₅O₃+3H₂O→3C₁₇H₃₃COOH+C₃H₈O₃ (glycerol)

When water is present in the reaction, it generally manifests itselfthrough excessive soap production. The soaps of saturated fatty acidstend to solidify at ambient temperatures and form a semi-solid mass verydifficult to recover.

A technical solution proposed to produce bio-destillates from feedstockwith high FFA content is to start with an acid catalyzedinteresterification with additional glycerol to convert FFA's intoglycerides prior to the basic transesterification. This process causes aredistribution of the fatty acids on the glycerol fragment of themolecule. This rearrangement process does not change the composition ofthe fatty acids from the starting materials. Interesterification may beaccomplished by chemical or enzymatic processes. Chemicalinteresterification is a process by which fatty acids are randomlydistributed across the glycerol backbone of the triglycerides. Thisprocess is carried out by blending the desired oils, drying them andadding a catalyst such as sodium methoxide. When the reaction iscomplete, the catalyst is neutralized and the rearranged product iswashed, bleached, and deodorized to give a final oil product withdifferent characteristics than the original oil blends. The secondprocess is enzymatic interesterification. This process rearranges thefatty acids on the glycerol backbone of the triglycerides through theuse of an enzyme. Higher temperature will results in inactivation of theenzyme. After interesterification, the oil is deodorized to makefinished oil products.

Chemical conversion of the oil to its corresponding fatty ester iscalled transesterification. This bio-distillate reaction requires acatalyst such as sodium hydroxide to split the oil molecules from thetriglycerides and an alcohol to combine with separated acyl-moiety. Themain byproduct is glycerol. One popular process for producingbio-destillates from fats and oils is transesterification oftriglyceride with methanol to make methyl esters of straight chain fattyacid according to the following reaction:

[C₁₈H₃₃O]₃C₃H₅O₃+3CH₃OH→3C₁₇H₃₃COOCH₃+C₃H₈O₃

The transesterification reaction proceeds well in the presence of somehomogeneous catalysts such as potassium hydroxide, sodium hydroxide,potassium-methoxide, sodium-methoxide and sulphuric acid, orheterogeneous catalysts such as metal oxides or carbonates.

Transesterification is the process of exchanging the alkoxy group of anester compound by another alcohol. These reactions are often catalyzedby the addition of a base and acid. Bases can catalyze the reaction byremoving a proton from the alcohol, thus making it more reactive, whileacids can catalyze the reaction by donating a proton to the carbonylgroup, thus making it more reactive.

Vegetable oils can be transesterified by heating them with a largeexcess of anhydrous methanol and a catalyst. More information abouttransesterification with catalyst using alkali's, acids or enzymes canbe found in literature (“The Biodiesel Handbook”, Gerhard Knothe, JonVan Gerpen, Jürgen Krahl, 2005 AOCS Press).

Obtention of Bio-Naphtha from Phase S

Three options exist to convert phase S fats & oils into LPG andnaphtha-like hydrocarbons that can be used for the steamcracking inorder to produce light olefins, dienes and aromatics. These aresummarised in table 3.

TABLE 3 Catalyst/intermediate Feedstock Process compounds Triglycerides,Catalytic Supported Ni, Mo, Co, eventually contain- Hydro- NiW, NiMo,CoMo, NiCoW, ing fatty acids deoxygenation NiCoMo, NiMoW and CoMoW Fattyacids Catalytic oxides or sulphides Decarboxylation Supported group 10(Ni, Pt, Pd) or group 11 (Cu, Ag) metals or alloys Basic oxides or mixedbasic oxides Fatty acids Soaps Thermal Soaps of alkali, alkalineDecarboxylation earth, lanthanides or group 12 or 13

The first option consists in hydrodeoxygenation, which removes theoxygen atoms from the fats & oils. This can be done on the triglyceridesas such, the triglycerides containing FFA's or on only FFA's.Hydrodeoxygenation of fats & oils has been reported in 1989 (W. H. Craigand D. W. Soveran, “Production of hydrocarbons with relatively highcetane rating”, U.S. Pat. No. 4,992,605 and Gusmao J, Brodzki D,Djéga-Mariadassou G, Frety R., “Utilization of vegetable oils as analternative source for diesel-type fuel: Hydrocracking on reducedNi/SiO2 and sulphided Ni—Mo/γ-Al2O3”, Cat, Today 1989 (5) 533) in whichconventional CoMo or NiMo sulphided catalysts are used. These catalystsare well known in hydrodesulphurization and are know to catalyze alsohydrodeoxygenation (E. Furimsky, Applied Catalysis A, General, 199,pages 147-190, 2000).

Hydrodeoxygenation of fats & oils is preferentially done in continuousfixed bed reactors, continuous stirred tank reactors or slurry typereactors containing solid catalyst that can be selected among Ni, Mo, Coor mixtures like NiW, NiMo, CoMo, NiCoW, NiCoMo, NiMoW and CoMoW oxidesor sulphides as catalytic phase, preferably supported on high surfacearea carbon, alumina, silica, titania or zirconia. It is preferred thatthe support for the catalytic active phase exhibit low acidity,preferable neutral or basic in order to avoid hydro-isomerisationreactions that would result in branched paraffin's and cracking atelevated temperature and pressure in the presence of hydrogen.Temperature ranges from 200 to 500° C., pressure from 1 MPa to 10 MPa(10 to 100 bars) and hydrogen to oil feed ratio from 100 to 2000 Nm³/m³of liquid. For optimum performance and stable continuous operation, itis preferred that the active metal component of the catalyst is in theform of sulfides. Thereto, it is preferred that traces amounts ofdecomposable sulphur compounds are present or added on purpose to thefeedstock in order to keep the metal sulphide in its sulphide state. Byway of example, these sulphur compounds can be H₂S, COS, CS₂, mercaptans(e.g. methylsulfide), thio-ethers (e.g. DiMethylSulfide), disulfides(e.g. DiMethyldiSulfide), thiophenic and tetrahydrothiophenic compounds.

Under hydrodeoxygenation conditions several reactions occur. The easiestis the hydrogenation of the double bonds in the alkyl-chain. The moredifficult reaction is the removal of oxygen atoms from the C—O bonds.Both the carboxyl-group of the fatty acid as the hydroxyl-group of theglycerol-moiety are hydrodeoxygenated. This results in the production oflinear paraffin, resulting from the fatty acid and in propane, resultingfrom glycerol. Depending on the conditions (catalyst, temperature,hydrogen etc), the carboxyl-group can also be decomposed into CO/CO₂(decarboxylation) and which on their turn can be even furtherhydrogenated into methane. These hydrodeoxygenation reactions consume alot of hydrogen.

As way of example is given the equation for triolein hydrodeoxygenation:

[C₁₈H₃₃O]₃C₃H₅O₃+15H₂→3C₁₈H₃₈+C₃H₈+6H₂O

Hydrodeoxygenation of fatty acids:

R—CH₂—CH₂—COOH+3H₂→3R—CH₂—CH₂—CH₃+2H₂O

Further hydrogenation of the intermediate CO/CO₂ can occur depending onthe amount of available hydrogen, the catalyst and the operatingconditions:

CO+3H₂→CH₄+H₂O

CO₂+4H₂→CH₄+2H₂O

The second option consists in decarboxylation or decarbonylation offatty acids. These fatty acids can be obtained from fats & oils byphysical refining (including steam/vacuum distillation), by (steam)splitting of triglycerides or by splitting of soaps (acidulation) usingacids. Decarboxylation of carboxylic acids has been reported in 1982 (W.F. Maier, Chemische Berichte, 115, pages 808-812, 1982) over Pd/SiO₂ andNi/Al₂O₃ catalysts in the gas phase. A highly selective decarboxylationhas been reported in 2005 (I. Kubickova, Catalysis Today, 106, pages197-200, 2005 and M. Snare, Industrial Engineering, Chemistry Research,45, p. 5708-5715, 2006) using transition metal catalysts. Palladiumbased catalysts exhibit the highest selectivity towards decarboxylation.Carboxylic acids can also be decarboxylated under catalytic conditionsusing basic catalyst, like MgO, ZnO and mixed basic oxides (A. Zhang *,Q. Ma, K. Wang, X. Liu, P. Shuler, Y. Tang, “Naphthenic acid removalfrom crude oil through catalytic decarboxylation on magnesium oxide”,Applied Catalysis A: General 303, p. 103, 2006; A. More, John R. Schlup,and Keith L. Hohn “Preliminary Investigations of the CatalyticDeoxygenation of Fatty Acids”, AIChe, The 2006 annual meeting, SanFrancisco and B. Kitiyanan, C. Ung-jinda, V. Meeyoo, “Catalyticdeoxygenation of oleic acid over ceria-zirconia catalysts”, AIChe The2008 annual meeting).

The following reactions can occur:

Decarboxylation:

R—CH₂—CH₂—COOH→R—CH₂—CH₃+CO₂

Decarbonylation:

R—CH₂—CH₂—COOH→R—CH═CH₂+CO+H₂O

Decarboxylation is preferentially done in presence of solid catalyst inbatch type tank reactors, continuous fixed bed type reactors, continuousstirred tank reactors or slurry type reactors. The catalyst can beselected among Ni, Mo, Co or mixtures like NiW, NiMo, CoMo, NiCoW,NiCoMo, NiMoW and CoMoW oxides or sulphides as catalytic phase,preferably supported on high surface area carbon, alumina, silica,titania or zirconia or group 10 (Ni, Pt and Pd) and group 11 (Cu and Ag)metals or alloy mixtures supported on high surface area carbon,magnesia, zinc-oxide, spinels (Mg₂Al₂O₄, ZnAl₂O₄), perovskites (BaTiO₃,ZnTiO₃), calciumsilicates (like xonotlite), alumina, silica orsilica-alumina's or mixtures of the latter. It is preferred that thesupport for the catalytic active phase exhibit low acidity, preferableneutral or basic in order to avoid hydro-isomerisation reactions thatwould result in branched paraffin's and cracking. Decarboxylation canalso be carried out on basic oxides, like alkaline oxides, alkalineearth oxides, lanthanide oxides, zinc-oxide, spinels (Mg₂Al₂O₄,ZnAl₂O₄), perovskites (BaTiO₃, ZnTiO₃), calciumsilicates (likexonotlite), either as bulk material or dispersed on neutral or basiccarriers, on basic zeolites (like alkali or alkaline earth lowsilica/alumina zeolites obtained by exchange or impregnation).

Although, the decarboxylation reaction does not require hydrogen, it ispreferred that the decarboxylation is done in presence of hydrogen thatwill stabilise the catalytic activity by removing strongly adsorbedunsaturated species (for instance when decarbonylation is the prevalentreaction pathway) from the catalyst surface by hydrogen-additionreactions. The presence of hydrogen can also hydrogenate the doublebonds present in the acyl-moiety of the fatty acid in order to obtainparaffinic reaction products from the decarboxylation process. Thedecarboxylation of the fatty acids can be carried out at 100 to 550° C.in absence or presence of hydrogen at pressures ranging from 0.01 up to10 MPa. The hydrogen to feedstock ratio is from 0 to 2000 Nl/l.

Other reactions that can occur under the decarboxylation conditions are:

R—CH═CH₂+H₂→R—CH₂—CH₃

Hydrodeoxygenation of fatty acids:

R—CH₂—CH₂—COOH+3H₂→R—CH₂—CH₂—CH₃+2H₂O

Further hydrogenation of the intermediate CO/CO₂ can occur depending onthe amount of available hydrogen, the catalyst and the operatingconditions:

CO+3H₂→CH₄+H₂O

CO₂+4H₂→CH₄+2H₂O

A third option to obtain bio-naphtha from fats & oils is through thethermal decarboxylation of soaps of fatty acids. The soaps can beobtained from the chemical refining of fats & oils by neutralisation,producing refined triglycerides and soaps, by neutralisation of fattyacids obtained after (steam) splitting of fats & oils or by directsaponification of fats & oils using basic oxides or basic hydroxides,producing a soap and glycerol.

Decarboxylation has been carried out by decomposition of fatty acids inhot compressed water with the aid of alkali-hydroxides, resulting in theproduction of alkanes and CO₂ (M. Watanabe, Energy Conversion andManagement, 47, p. 3344, 2006). Calcium-soaps of Tung oil have beenreported to decompose by distillation as early as 1947 (C. C, Chang, S.W, Wan, “China's Motor Fuels from Tung Oil”, Ind. Eng. Chem., 39 (12),p. 1543, 1947; Hsu, H. L., Osburn, J. O., Grove, C. S., “Pyrolysis ofthe calcium salts of fatty acids”, Ind. Eng. Chem. 42(10), p. 2141,1950; Craveiro, A. A.; Matos, F. J. A.; Alencar, J. W.; Silveira E. R.Energia: Fontes Alternativas 3, p. 44, 1981; A. Demirbas, “Diesel fuelfrom vegetable oil via transesterification and soap pyrolysis”, EnergySources 24 9, p. 835, 2002).

The preferred soaps are those made of alkaline, alkaline earth,lanthanide, zinc or aluminium cations. The thermal decarboxylation ofsoap can be carried out by heating until the molten soap starts todecompose into the corresponding paraffin's or olefins and thecorresponding metal-carbonate or metal-oxide/hydroxide and CO₂. Withoutwilling to be bound to any theory, it is believed that the followingoverall reactions occur:

[R—CH₂—CH₂—COO⁻]_(x)M^(x+) +xH₂O→xR—CH₂—CH₃+M[HCO₃]_(x)

M[HCO₃]_(x)←→M[OH]_(x)+CO₂

It is preferred that the thermal decomposition of the soaps is carriedout in the presence of liquid, supercritical or vaporous water.

Steamcracking

Steamcrackers are complex industrial facilities that can be divided intothree main zones, each of which has several types of equipment with veryspecific functions: (i) the hot zone including: pyrolysis or crackingfurnaces, quench exchanger and quench ring, the columns of the hotseparation train (ii) the compression zone including: a cracked gascompressor, purification and separation columns, dryers and (iii) thecold zone including: the cold box, de-methaniser, fractionating columnsof the cold separation train, the C₂ and C₃ converters, the gasolinehydrostabilization reactor Hydrocarbon cracking is carried out intubular reactors in direct-fired heaters (furnaces). Various tube sizesand configurations can be used, such as coiled tube, U-tube, or straighttube layouts. Tube diameters range from 1 to 4 inches. Each furnaceconsists of a convection zone in which the waste heat is recovered and aradiant zone in which pyrolysis takes place. The feedstock-steam mixtureis preheated in the convection zone to about 530-650° C. or thefeedstock is preheated in the convection section and subsequently mixedwith dilution steam before it flows over to the radiant zone, wherepyrolysis takes place at temperatures varying from 750 to 950° C. andresidence times from 0.05 to 0.5 second, depending on the feedstock typeand the cracking severity desired. In an advantageous embodiment theresidence time is from 0.05 to 0.15 second. The steam/feedstock (thesteam/[hydrocarbon feedstock]) weight ratio is between 0.2 and 1.0kg/kg, preferentially between 0.3 and 0.5 kg/kg. In an advantageousembodiment the steam/feedstock weight ratio is between 0.2 and 0.45 andpreferably between 0.3 and 0.4. For steamcracking furnaces, the severitycan be modulated by:

temperature, residence time, total pressure and partial pressure ofhydrocarbons. In general the ethylene yield increases with thetemperature while the yield of propylene decreases. At hightemperatures, propylene is cracked and hence contributes to moreethylene yield. The increase in severity thus obtained leads to amoderate decrease in selectivity and a substantial decrease of the ratioC₃═/C₂═. So high severity operation favors ethylene, while low severityoperation favors propylene production. The residence time of the feed inthe coil and the temperature are to be considered together. Rate of cokeformation will determine maximum acceptable severity. A lower operatingpressure results in easier light olefins formation and reduced cokeformation. The lowest pressure possible is accomplished by (i)maintaining the output pressure of the coils as close as possible toatmospheric pressure at the suction of the cracked gas compressor (ii)reducing the pressure of the hydrocarbons by dilution with steam (whichhas a substantial influence on slowing down coke formation). Thesteam/feed ratio must be maintained at a level sufficient to limit cokeformation.

Effluent from the pyrolysis furnaces contains unreacted feedstock,desired olefins (mainly ethylene and propylene), hydrogen, methane, amixture of C₄'s (primarily isobutylene and butadiene), pyrolysisgasoline (aromatics in the C₆ to C₈ range), ethane, propane, di-olefins(acetylene, methyl acetylene, propadiene), and heavier hydrocarbons thatboil in the temperature range of fuel oil. This cracked gas is rapidlyquenched to 338-510° C. to stop the pyrolysis reactions, minimizeconsecutive reactions and to recover the sensible heat in the gas bygenerating high-pressure steam in parallel transfer-line heat exchangers(TLE's). In gaseous feedstock based plants, the TLE-quenched gas streamflows forward to a direct water quench tower, where the gas is cooledfurther with recirculating cold water. In liquid feedstock based plants,a prefractionator precedes the water quench tower to condense andseparate the fuel oil fraction from the cracked gas. In both types ofplants, the major portions of the dilution steam and heavy gasoline inthe cracked gas are condensed in the water quench tower at 35-40° C. Thewater-quench gas is subsequently compressed to about 25-35 Bars in 4 or5 stages. Between compression stages, the condensed water and lightgasoline are removed, and the cracked gas is washed with a causticsolution or with a regenerative amine solution, followed by a causticsolution, to remove acid gases (CO₂, H₂S and SO₂). The compressedcracked gas is dried with a desiccant and cooled with propylene andethylene refrigerants to cryogenic temperatures for the subsequentproduct fractionation: Front-end demethanization, Front-enddepropanization or Front-end deethanization.

In a front-end demethanization configuration, tail gases (CO, H₂, andCH₄) are separated from the C₂+ components first by de-methanizationcolumn at about 30 bars. The bottom product flows to thede-ethanization, of which the overhead product is treated in theacetylene hydrogenation unit and further fractionated in the C₂splitting column. The bottom product of the de-ethanization goes to thede-propanization, of which the overhead product is treated in the methylacetylene/propadiene hydrogenation unit and further fractionated in theC₃ splitting column. The bottom product of the de-propaniser goes to thede-butanization where the C₄'s are separated from the pyrolysis gasolinefraction. In this separation sequence, the H₂ required for hydrogenationis externally added to C₂ and C₃ streams. The required H₂ is typicallyrecovered from the tail gas by methanation of the residual CO andeventually further concentrated in a pressure swing adsorption unit.

Front-end de-propanization configuration is used typically insteamcrackers based on gaseous feedstock. In this configuration, afterremoving the acid gases at the end of the third compression stage, theC₃ and lighter components are separated from the C₄₊ byde-propanization. The de-propanizer C₃− overhead is compressed by afourth stage to about 30-35 bars. The acetylenes and/or dienes in theC₃− cut are catalytically hydrogenated with H₂ still present in thestream. Following hydrogenation, the light gas stream is de-methanized,de-ethanized and C₂ split. The bottom product of the de-ethanization caneventually be C₃ split. In an alternative configuration, the C₃−overhead is first de-ethanised and the C₂− treated as described abovewhile the C₃'s are treated in the C₃ acetylene/diene hydrogenation unitand C₃ split. The C₄+ de-propanizer bottom is de-butanized to separateC₄'s from pyrolysis gasoline.

There are two versions of the front-end de-ethanization separationsequence. The product separation sequence is identical to the front-endde-methanization and front-end depropanization separation sequence tothe third compression stage. The gas is de-ethanized first at about 27bars to separate C₂− components from C₃+ components. The overhead C₂−stream flows to a catalytic hydrogenation unit, where acetylene in thestream is selectively hydrogenated. The hydrogenated stream is chilledto cryogenic temperatures and de-methanized at low pressure of about9-10 bars to strip off tail gases. The C₂ bottom stream is split toproduce an overhead ethylene product and an ethane bottom stream forrecycle. In parallel, the C₃+bottom stream from the front-endde-ethanizer undergoes further product separation in a de-propaniser, ofwhich the overhead product is treated in the methyl acetylene/propadienehydrogenation unit and further fractionated in the C₃ splitting column.The bottom product of the de-propaniser goes to the de-butanizationwhere the C₄'s are separated from the pyrolysis gasoline fraction. Inthe more recent version of the front-end de-ethanization separationconfiguration, the cracked gas is caustic washed after three compressionstages, pre-chilled and is then de-ethanized at about 16-18 bars toppressure. The net overhead stream (C₂−) is compressed further in thenext stage to about 35-37 bars before it passes to a catalytic converterto hydrogenate acetylene, with hydrogen still contained in the stream.Following hydrogenation, the stream is chilled and de-methanized tostrip off the tail gases from the C₂ bottom stream. The C₂'s are splitin a low pressure column operating at 9-10 bars pressure, instead of19-24 bars customarily employed in high pressure C₂ splitters that use apropylene refrigerant to condense reflux for the column. For thelow-pressure C₂ splitter separation scheme, the overhead cooling andcompression system is integrated into a heat-pump, open-cycle ethylenerefrigeration circuit. The ethylene product becomes a purged stream ofthe ethylene refrigeration recirculation system.

The ethane bottom product of the C₂ splitter is recycled back to steamcracking. Propane may also be re-cracked, depending on its market value.Recycle steam cracking is accomplished in two or more dedicatedpyrolysis furnaces to assure that the plant continues operating whileone of the recycle furnaces is being decoked.

Many other variations exist of the above-described configurations, inparticular in the way the undesired acetylene/dienes are removed fromthe ethylene and propylene cuts.

The different embodiments are represented in FIGS. 3 to 5.

In a first embodiment (FIG. 3), Fats & Oils are physically refined byvacuum distillation or steam distillation (10) to recover the mixedfatty acids (12) as overhead product and the triglycerides (11) asbottom product. Either the fats & oils, eventually still containing freefatty acids (21) or the physically refined triglycerides (20) acids arefractional crystallised (according to FIG. 2), resulting in a phase Sand a phase L fraction and the phase S can be sent to ahydrodeoxygenation section (22) where they are converted intobio-naphtha (31) and bio-propane (30). This bio-naphtha (41) andbio-propane (43) are sent to the to steamcracking (50) or blended withfossil LPG, naphtha or gasoil (40) and hence the blend is streamcracked(50). The products of the steamcracking are cooled, compressed,fractionated and purified (51). This results in light olefins (ethylene,propylene and butenes), dienes (butadiene, isoprene, (di)cyclopentadieneand piperylenes), aromatics (benzene, toluene and mixed xylenes) andgasoline as main components. The phase L, obtained from the fractionalcrystallisation (23) is sent to biodiesel production section (25).

In a second embodiment (FIG. 4), Fats & Oils are physically refined byvacuum distillation or steam distillation (10) to recover the mixedfatty acids (12) as overhead product and the triglycerides (11) asbottom product. Optionally, the triglycerides are sent to the fractionalcrystallisation section (15). The fats & oils, and optionally thetriglycerides, obtained from the physical refining (15) are fractionalcrystallised (21) and the phase S fraction is optionally hydrolysed (26)to produce mixed fatty acids (28) and glycerol (27). The mixed fattyacids can be sent (30) to a hydrodeoxygenation section where they areconverted into bio-naphtha (36) or alternatively they can be sent to thedecarboxylation section (31) where they are converted into bio-naphtha(35). This bio-naphtha (41) is sent to the to steamcracking (50) orblended with fossil LPG, naphtha or gasoil (40) and hence the blend isstreamcracked (50). The products of the steamcracking are cooled,compressed, fractionated and purified (51). This results in lightolefins (ethylene, propylene and butenes), dienes (butadiene, isoprene,(di)cyclopentadiene and piperylenes), aromatics (benzene, toluene andmixed xylenes) and gasoline as main components. The phase L, obtainedfrom the fractional crystallisation (23) is sent to biodiesel productionsection (25).

In a third embodiment (FIG. 5), fats & Oils are fractional crystallised(21) and the phase S fraction saponificated (27) to recover the soap(22) and glycerol (23). Optionally phase S, obtained by fractionalcrystallisation of fats & Oils can be hydrolysed (24) to produce mixedfatty acids (28) and glycerol (26). Alternatively, soap (25) can beobtained during a chemical refining step of raw fats & oils (24) by theneutralisation step. Still another source of soap (30) is vianeutralisation (29) of fatty acids, obtained by (steam) splitting (24)of fractional crystallised fats & oils, producing fatty acids (28) andglycerol (26). The soaps can be sent (31) to the decarboxylation sectionwhere they are converted into bio-naphtha (35) and metal-carbonates orCO₂ (36). This bio-naphtha (41) is sent to the to steamcracking (50) orblended with fossil LPG, naphtha or gasoil (40) and hence the blend isstreamcracked (50). The products of the steamcracking are cooled,compressed, fractionated and purified (51). This results in lightolefins (ethylene, propylene and butenes), dienes (butadiene, isoprene,(di)cyclopentadiene and piperylenes), aromatics (benzene, toluene andmixed xylenes) and gasoline as main components. The phase L, obtainedfrom the fractional crystallisation (23) is sent to biodiesel productionsection (25).

EXAMPLES Example 1

Hydrodeoxygenation of a triglyceride feed has been evaluated under thefollowing conditions:

In an isothermal reactor, 10 ml of a hydrotreating catalyst composed ofMolybdenum and Nickel supported on alumina (KF848 obtained fromAlbemarle) was loaded, the catalyst dried and pre-sulfurised understandard conditions with straightrun gasoil doped with DMDS. Thehydrodeoxygenation of rapeseed is done at:

LHSV=1 h⁻¹

Inlet Temperature=320° C.

Outlet pressure=60 bars

H2/oil ratio=630 Nl/l

Feedstock=rapeseed doped with 1 wt % DMDS

Table 4 shows a typical composition of the rapeseed oil.

The gas and liquid effluent are separated by means of a separator(gas/liquid) at atmospheric pressure. Gases are sent to a μ-GC analyserand liquids are sent to a sampler. The mass balance is around 99% andall product weights are calculated for 100 g of treated feed.

TABLE 4 Typical composition of rapeseed oil Components wt %tetradecanoate 0.1 hexadecenoate 0.2 hexadecanoate 4.8 heptadecanoate0.1 octadecadienoate 20.6 octadecenoate 61.3 octadécatrienoate 8.6octadecanoate 1.8 eisosenoate 1.2 eicosanoate 0.7 docosenoate 0.3docosanoate 0.3 100

The total liquid effluent is biphasic and need a separation step. Theorganic phase was analyzed via GC-MS. A complete analysis is reported intable 5.

The liquid effluent is composed of 94.4 wt % of n-paraffins but it iscomposed of 99.94 wt % of interesting components, which could be sent tothe naphtha-cracker.

TABLE 5 Material balance and complete GC analysis of hydro carbon phaseFeed Products 5.96 gr hydrogen 6.48 gr CO2 100 gr rapeseed 0.55 gr CO3.52 H2 5.98 gr propane 0.18 gr methane 2.77 gr water phase 85 grhydrocarbon phase Hydrocarbon phase composition Wt % C3 0.005n-paraffin's with C₅ to C₁₄ 0.268 other paraffin's with C₅ to C₁₄ 0.238other C15 0.061 n-C15 2.353 other C16 0.100 n-C16 2.754 other C17 1.633n-C17 41.077 other C18 2.108 n-C18 44.344 dodecyl-cyclohexane 0.168tridecyl-cyclopentane 0.110 n-paraffin's with C₁₉ to C₃₅ 3.599 otherparaffin's with C₁₉ to C₃₅ 1.1 >n-C35 0.013 2-butanone 0.034 Otheroxygenates 0.025 Total 100.00

94.4 wt % of the hydrocarbon phase are comprised of n-paraffin's that ishigh quality bio-naphtha feedstock for a steamcracker. About 0.059 wt %of remaining oxygenates are found in the hydrocarbon phase. Thatcorresponds to 112 wppm O-atoms. Considering the O content in thetriglyceride feed, that represents 10.86 wt % (or 108600 wppm O-atoms),resulting in a hydrodeoxygenation conversion of 99.89%.

Example 2

n-Paraffin's and conventional naphtha have been steamcracked underdifferent severity conditions. Table 6 gives the results. It is evidentfrom the results that such-obtained bio-naphtha are better feedstock forsteamcracking compared to fossil naphtha.

Significant higher ethylene and propylene yields can be obtained whereasthe methane make and the pyrolysis gasoline make is reduced with atleast about 20%. The ultimate yield of HVC (High valueChemicals=H2+ethylene+propylene+butadiene+benzene) is above 70 wt %.Ethylene/Methane weight ratio is always above 3.

TABLE 6 Naphtha n-Decane n-C15 n-C20 Naphtha n-Decane n-C15 n-C20 P/E0.59 0.44 0.50 0.49 0.50 0.39 0.44 0.44 COT 812 812 812 812 832 832 832832 S/HC 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 Summary wt % (dry) wt %(dry) wt % (dry) wt % (dry) wt % (dry) wt % (dry) wt % (dry) wt % (dry)Hydrogen 0.87 0.66 0.59 0.57 0.96 0.76 0.69 0.67 Methane 14.79 11.6710.65 10.00 16.25 12.80 11.80 11.15 Acetylene 0.25 0.25 0.25 0.25 0.360.37 0.37 0.37 Ethylene 25.39 38.87 36.24 35.82 26.91 39.67 36.93 36.47Ethane 4.09 6.58 6.07 5.84 3.89 6.10 5.62 5.42 Methyl-Acetylene 0.290.21 0.22 0.22 0.36 0.26 0.27 0.27 Propadiene 0.21 0.15 0.16 0.16 0.250.18 0.19 0.19 Propylene 15.10 17.29 18.08 17.63 13.48 15.59 16.28 15.91Propane 0.51 0.73 0.69 0.66 0.44 0.62 0.59 0.57 Vinyl-Acetylene 0.040.04 0.04 0.04 0.05 0.06 0.07 0.07 Butadiene 4.61 5.96 6.88 7.30 4.415.79 6.49 6.79 Butene (sum) 4.86 2.99 3.34 3.43 3.67 2.12 2.34 2.38Butane (sum) 0.08 0.14 0.12 0.12 0.06 0.11 0.09 0.09 Total C5-C9's 23.6912.48 14.65 15.75 22.30 13.14 15.33 16.42 Total C10+ 5.17 1.93 1.96 2.156.53 2.38 2.86 3.18 Carbon Oxide 0.05 0.05 0.05 0.05 0.07 0.07 0.07 0.07Carbon Dioxide 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.00 Ultimate Ethylene28.67 44.14 41.09 40.49 30.02 44.55 41.43 40.80 C2= + C3= 43.77 61.4359.17 58.12 43.51 60.14 57.71 56.70 BENZENE 8.27 5.35 6.46 7.05 9.426.55 7.77 8.39 HVG's 54.25 68.14 68.24 63.37 55.18 68.35 68.16 68.23Ultimate HVC's 57.52 73.40 73.10 73.04 58.29 73.23 72.66 72.56 P/E isthe propylene/ethylene ratio COT is the coil outlet temperature S/HC isthe ratio steam/hydrocarbon Naphtha composition wt % Normal paraffins31.26 Iso paraffins 33.48 Naphtenics 28.1 Aromatics 7.16 Olefins 0Others 0

1. Process for making a bio-diesel and a bio-naphtha and optionallybio-propane from a complex mixture of natural occurring fats & oils,wherein said complex mixture is subjected to a refining treatment forremoving the major part of the non-triglyceride and non-fatty acidcomponents, thereby obtaining refined oils; said refined oils aresubjected to a fractionation step for obtaining: an unsaturated orsubstantially unsaturated, liquid or substantially liquid triglyceridepart (phase L); and a saturated or substantially saturated, solid orsubstantially solid triglyceride part (phase S); and said phase L istransformed into alkyl-esters as bio-diesel by a transesterification;said phase S is transformed into linear or substantially linearparaffin's as the bio-naphtha: by an hydrodeoxygenation or from saidphase S are obtained fatty acids that are transformed into linear orsubstantially linear paraffin's as the bio-naphtha by hydrodeoxygenationor decarboxylation of the free fatty acids or from said phase S areobtained fatty acids soaps that are transformed into linear orsubstantially linear paraffin's as the bio-naphtha by decarboxylation ofthe soaps.
 2. The process according to claim 1, wherein said complexmixture of natural occurring fats & oils is selected among vegetableoils and animal fats, preferentially inedible oils, highly saturatedoils, waste food oils, by-products of the refining of vegetable oils,and mixtures thereof.
 3. The process according to claim 1, wherein saidfatty acids are obtained by physical refining, including a steamdistillation or vacuum distillation of fats & oils or said fatty acidsare obtained by hydrolysis of triglycerides of the fats & oils or saidfatty acids are obtained by acidulation of soaps.
 4. The processaccording to anyone of claim 1, wherein said refined oils are fractionedinto said phases L and S by a fractional crystallisation method whichconsists in a controlled cooling down during which the triglycerides ofsaid complex mixture with substantially saturated acyl-moietiescrystallize and precipitate from the mixture forming said phase S, whilethe triglycerides with substantially unsaturated acyl-moieties remainliquid forming said phase L, both phases being then separated by simplefiltration or decantation or centrifugation.
 5. The process according toclaim 1, wherein said phase L is transesterified with a C₁-C₅monofunctional alcohol in order to produce alkyl fatty esters asbio-diesel and glycerol.
 6. The process according to claim 1, whereinsaid fatty acid soaps are obtained by saponification of fats & oils orby the chemical refining, including neutralisation of free fatty acids,present in the fats & oils or neutralisation of fatty acids, obtainedfrom hydrolysis of the fats & oils
 7. The process according to anyone ofclaim 1, wherein said phase S is transformed into linear orsubstantially linear paraffins as bio-naphtha together with bio-propaneby hydrodeoxygenation in the presence of hydrogen and of at least onecatalyst that can be selected among Ni, Mo, Co or mixtures like NiW,NiMo, CoMo, NiCoW, NiCoMo, NiMoW and CoMoW oxides or sulphides ascatalytic phase, preferably supported on high surface area carbon,alumina, silica, titania or zirconia.
 8. The process according to claim7, wherein the hydrodeoxygenation is carried out at a temperature from200 to 500° C., under a pressure from 1 MPa to 10 MPa (10 to 100 bars)and with a hydrogen to feed ratio from 100 to 2000 Nl/l.
 9. The processaccording to anyone of claim 1, wherein said phase S is transformed intolinear or substantially linear paraffins as bio-naphtha by hydrolysisinto glycerol and fatty acids, removal of the glycerol or by physicalrefining, including a steam distillation or vacuum distillation of fats& oils or obtained by acidulation of soaps and hydrodeoxygenation ordecarboxylation of the fatty acids, said hydrodeoxygenation ordecarboxylation being conducted in the presence of hydrogen and of atleast one catalyst that can be selected among Ni, Mo, Co or mixtureslike NiW, NiMo, CoMo, NiCoW, NiCoMo, NiMoW and CoMoW oxides or sulphidesas catalytic phase, preferably supported on high surface area carbon,alumina, silica, titania or zirconia or group 10 (Ni, Pt and Pd) andgroup 11 (Cu and Ag) metals or alloy mixtures supported on high surfacearea carbon, magnesia, zinc-oxide, spinels (Mg₂Al₂O₄, ZnAl₂O₄),perovskites (BaTiO₃, ZnTiO₃), calciumsilicates (like xonotlite),alumina, silica or silica-alumina's or mixtures of the latter.
 10. Theprocess according to anyone of claim 1, wherein said phase S istransformed into linear or substantially linear paraffin's asbio-naphtha by hydrolysis into glycerol and fatty acids, removal of theglycerol or by physical refining, including a steam distillation orvacuum distillation of fats & oils or obtained by acidulation of soapsand decarboxylation of the fatty acids is carried out on basic oxides,like alkaline oxides, alkaline earth oxides, lanthanide oxides,zinc-oxide, spinels (Mg₂Al₂O₄, ZnAl₂O₄), perovskites (BaTiO₃, ZnTiO₃),calciumsilicates (like xonotlite), either as bulk material or dispersedon neutral or basic carriers, on basic zeolites (like alkali or alkalineearth low silica/alumina zeolites obtained by exchange or impregnation).11. The process according to anyone of claim 7, wherein thehydrodeoxygenation is carried out at a temperature from 200 to 500° C.,under a pressure from 1 MPa to 10 MPa (10 to 100 bars) and with ahydrogen to feedstock ratio from 100 to 2000 Nl/l, or wherein thedecarboxylation is carried out at a temperature from 100 to 550° C.,under a pressure from 0.1 MPa to 10 MPa (1 to 100 bars) and with ahydrogen to feedstock ratio from 0 to 2000 Nl/l.
 12. The processaccording to claim 1, wherein the decarboxylation of the soaps iscarried out at from 100 to 550° C. under pressure from 0.1 Mpa to 10 Mpaand in presence of water.
 13. The process according to claim 1, whereinthe decarboxylation of the soaps is carried out with a water tofeedstock ratio of at least 1 mole water per mole of soap.
 14. Use ofthe bio-naphtha as obtained in the process of claim 1, as a directfeedstock of a steamcracker, said bio-naphtha being used as such, oroptionally together with bio-propane, or as blended with at least aconventional feedstock selected among LPG, naphtha and gasoil, in orderto obtain cracked products including bio-ethylene, bio-propylene,bio-butadiene, bio-isoprene, bio-cyclopentadiene and bio-piperylenes,bio-benzene, bio-toluene, bio-xylene and bio-gasoline.
 15. The processfor steam cracking a feedstock as defined in claim 14, wherein saidfeedstock is mixed with steam in a ratio of 0.2 to 1.0 kg steam per kgfeedstock, preferentially of 0.3 to 0.5 kg steam per kg feedstock andthe mixture is heated up to a temperature of 750-950° C. at a residencetime of 0.05 to 0.5 seconds.
 16. Use of the bio-naphtha as obtained inthe process of claim 1 for steamcracking such as to obtain a ethylene tomethane weight ratio, resulting from the cracking of bio-naphtha, of atleast 3.